CN104525938B - Molybdenum disulfide/gold nanorod composite, preparation method and application - Google Patents
Molybdenum disulfide/gold nanorod composite, preparation method and application Download PDFInfo
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- CN104525938B CN104525938B CN201410815045.4A CN201410815045A CN104525938B CN 104525938 B CN104525938 B CN 104525938B CN 201410815045 A CN201410815045 A CN 201410815045A CN 104525938 B CN104525938 B CN 104525938B
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Abstract
The invention relates to a preparation method of a molybdenum disulfide/gold nanorod composite. The method includes the step that under the electrostatic action, electronegative molybdenum disulfide nanosheets and electropositive gold nanorods are combined to obtain the molybdenum disulfide/gold nanorod composite. The molybdenum disulfide/gold nanorod composite has good photo-thermal conversion performance, the preparation method of the molybdenum disulfide/gold nanorod composite is simple, operation is easy, and equipment requirements are low; the composite obtained through the preparation method is low in impurity content and high in yield, and the combination density of the gold nanorods is high on the basis of a molybdenum disulfide laminated structure.
Description
Technical field
The invention belongs to the preparation field of molybdenum disulfide nano material, it is related to a kind of molybdenum disulfide nano-composite material, system
Preparation Method and purposes, more particularly, to a kind of lamella molybdenum bisuphide/gold nanorods nano composite material, Preparation method and use.
Background technology
Thermotherapy (Photo-thermal Therapy, PTT) is the method by heating, and changes tumour cell local environment,
Make tumour cell denaturation, necrosis, reach therapeutic purposes.Heat energy produces different impacts to cell, and low dosage heat treatment contributes to
The recovery damaging, high dose heat treatment may lead to cell death, and medium, gentle, non-lethal dose heat treatment can make to swell
Oncocyte becomes sensitive to radiotherapy and many medicines.
Near infrared region (800～1200nm) is the transmission window of body tissue, and near infrared light is high in body tissue transmitance,
Compared with its all band, human body is damaged little, the material seeking to have good optical characteristic near infrared region is used for biomedical neck
Domain is always the ideal chose of people.
The laminar structured transition metal dichalcogenide of the tool such as molybdenum bisuphide, MX2(M=Mo, W；X=S, Se, Te), have
Excellent physicochemical properties, obtain the extensive concern of people in recent years.Molybdenum disulfide nano sheet not only can utilize specific surface
Long-pending big feature loads specific medicine or photosensitive molecular, and has obvious photothermal deformation ability near infrared region, in biology
The photo-thermal therapy aspect of medical science shows good application prospect.
Gold nanorods are because its uniqueness, adjustable surface plasma resonance characteristic and synthetic method are simple, chemical property
Stably, the advantages of yield is high is so as to biomedical and the aspect such as medical diagnosis on disease and treatment application is also more and more extensive.This
Outward, gold nanorods absorption near infrared light can produce heating behavior, and this has special superiority in the photo-thermal therapy of disease.
How the material with near-infrared heating behavior to be combined, obtained the more excellent composite wood of photo-thermal effect
Material, is the problem that this area needs to solve.
Content of the invention
An object of the present invention is to provide a kind of preparation method of molybdenum bisuphide/gold nanorods composite, described
Method is：In electronegative molybdenum disulfide nano sheet and self assembly in the aqueous solution will be placed in electropositive gold nanorods and be combined,
Obtain molybdenum bisuphide/gold nanorods composite.
In aqueous, rely on, in electronegative molybdenum disulfide nano sheet with electropositive gold nanorods, the electricity respectively carrying
Property, positive negative electricity is attracting, and self assembly obtains molybdenum bisuphide/gold nanorods composite.
Molybdenum disulfide nano sheet in negative potential of the present invention is n-layer nanometer sheet；Described n≤10, such as 1,2,3,4,
5th, 6,7,8,9 etc..
Preferably, molybdenum bisuphide liquid phase is peeled off by using remover and is obtained by the described molybdenum disulfide nano sheet in negative potential
?.
The present invention is not specifically limited for the preparation method of the molybdenum disulfide nano sheet in negative potential, any can prepare
The method obtaining the molybdenum disulfide nano sheet in negative potential is used equally to the present invention.
As optimal technical scheme, described it is prepared via a method which to obtain in electronegative molybdenum disulfide nano sheet：
(1), under protective atmosphere, add in molybdenum disulfide powder and peel off agent dispersing liquid, carry out liquid phase stripping reaction；
(2) reaction finishes, and adds solvent to reactant liquor, and layering takes precipitation；
(3) precipitation of step (2) is dispersed in certain solvent, ultrasonic, centrifugation, takes supernatant to be dialysed, obtain two
The molybdenum sulfide nanometer sheet aqueous solution.
Remover of the present invention is selected from n-BuLi and/or lithium chloride.
The mol ratio of molybdenum bisuphide of the present invention and remover is 1:2～8, such as 1:2.2、1:2.5、1:2.8、1:
3.4、1:3.9、1:4.6、1:5.7、1:6.2、1.7、1:7.6 waiting, preferably 3:8.
The dispersion solvent peeling off agent dispersing liquid of the present invention is selected from the saturated hydrocarbon solution such as n-hexane, hexamethylene, benzene
Any a kind or at least 2 kinds of combination；The combination of described combination such as n-hexane and benzene, the combination of hexamethylene and n-hexane, just own
Combination of alkane, hexamethylene and benzene etc..
The temperature of liquid phase stripping reaction of the present invention is 20～30 DEG C, such as 22 DEG C, 25 DEG C, 27 DEG C etc., preferably room temperature；
Reaction time 5～144h, such as 8h, 15h, 33h, 75h, 95h, 125h, 142h etc., preferably 48h.
Step (2) of the present invention described solvent stripping described with step (1) agent dispersing liquid dissolves each other.
The described solvent of step (3) of the present invention be selected from deionized water, methyl alcohol, ethanol, any a kind or at least 2 in isopropanol
The combination planted, the combination of described combination such as methyl alcohol and ethanol, the combination of ethanol and isopropanol, the combination of water and isopropanol, first
Alcohol, combination of second alcohol and water etc.；Preferably deionized water.
Preferably, the molecule interception of the described dialysis of step (3) is 14kDa；Dialysis time >=48h.
Preferably, described protective atmosphere is nonoxidizing atmosphere, preferably nitrogen atmosphere, helium atmosphere, neon atmosphere or argon
Any a kind in gas atmosphere or at least 2 kinds of combination.
Of the present invention prepared by the no seed law in electropositive gold nanorods；Preferably pass through step-by-step reduction chlorine gold
It is in electropositive gold nanorods that acid obtains.
The present invention is not specifically limited to the preparation method in electropositive gold nanorods, any is obtained in that in electropositive
Gold nanorods method be used equally to the present invention.
Preferably, described it is prepared via a method which to obtain in electropositive gold nanorods
(4) chlorauric acid solution is added in cetyl trimethylammonium bromide solution, stirs, add nitric acid afterwards
Silver-colored solution, stirs, and adds ascorbic acid solution, continues stirring colourless to solution；
(5) add sodium borohydride solution, standing reaction, centrifugation layering in the solution of step (4), take lower sediment to disperse
The gold nanorods aqueous solution is obtained in water.
The concentration of the described cetyl trimethylammonium bromide of step (4) of the present invention is 0.1mol/L；
Preferably, the mol ratio of described gold chloride and silver nitrate is 164～54:1, such as 55:1、68:1、72:1、90:1、
135:1、160:1 etc., preferably 82:1；
Preferably, the mol ratio of described gold chloride and ascorbic acid is 1:0.5～3, such as 1:0.5、1:1.3、1:1.5、
1:1.9、1:2.1、1:2.6、1:2.9 etc., preferably 5:4；
Preferably, the mol ratio of described gold chloride and sodium borohydride is 98～39:1, such as 80:1、50:1、45:1、39:1
Deng preferably 65:1；
Preferably, the time of described standing reaction is 1～12h, such as 2h, 3h, 6h, 7.5h, 10.2h etc., preferably 3h.
Recombination process in electronegative molybdenum disulfide nano sheet with electropositive gold nanorods of the present invention includes
Following steps：
(6) add the gold nanorods that step (5) obtains water-soluble in the molybdenum disulfide nano sheet aqueous solution obtaining to step (3)
Liquid mixes, and is reacted afterwards；
(7) reaction finishes, centrifugation, takes lower sediment to be dispersed in water and obtains molybdenum bisuphide/gold nanorods composite.
The mass ratio of the described molybdenum disulfide nano sheet of step (6) of the present invention and gold nanorods is 1:1.25～10, such as 1:
1.3、1:1.7、1:2.5、1:2.9、1:3.1、1:3.6、1:4.3、1:4.9、1:5.2、1:6.6、1:7.3、1:7.8、1:8.3、
1:8.8、1:9.3 etc., preferably 2:5.
Preferably, the described reaction time is 3～48h, such as 5h, 9h, 16h, 25h, 32h, 45h etc., preferably 24h.
It is added with mercapto-polyglycol (PEG-SH) in the molybdenum disulfide nano sheet aqueous solution described in step (6) of the present invention；
In the described molybdenum disulfide nano sheet aqueous solution, the mass concentration of mercapto-polyglycol is 0.5～1mg/mL.
Preferably, the described mixed process of step (6) is added with mercapto-polyglycol；In described mixed solution, sulfydryl
The mass concentration of polyethylene glycol is 0.5～1mg/mL.
Preferably, the molecular weight of described mercapto-polyglycol be 2000～10000, such as 2500,2800,3200,4000,
6000th, 8000,9000 etc., preferably 5000.
The present invention is modified to molybdenum disulfide nano sheet using mercapto-polyglycol, can lift molybdenum disulfide nano sheet
Stability in the solution, obtains dispersiveness and all preferable molybdenum bisuphide lamellar structure of stability.In addition, mercapto-polyglycol
Sulfydryl can the surface of gold nanorods formed Au-S key, improve the biocompatibility of gold nanorods.Therefore, the present invention exists
In the preparation process of molybdenum bisuphide/gold nanorods composite, add mercapto-polyglycol, substantially increase stablizing of material
Property, dispersiveness and biocompatibility.
The molybdenum disulfide nano-composite material providing as optional technical scheme, the present invention, i.e. molybdenum bisuphide/gold nanorods
The preparation method of composite comprises the steps：
A. it is in the preparation of the molybdenum disulfide nano sheet of negative potential
(1) weigh 500mg molybdenum disulfide powder (99%) to be placed in the round-bottomed flask that 10mL is dried, be passed through nitrogen, add
5mL 1.6mol/L dispersion n-BuLi in hexane, reacts 48h under room temperature；
(2), after reaction terminates, add hexane, diluting reaction solution, be centrifuged 10min；Disperse lower sediment with hexane, repeatedly
Centrifugation 2 times；
(3) take lower sediment disperse in aqueous, ultrasonic to bubble-free generation；Centrifugation 10min, removes lower floor, takes
Clear liquid, is dialysed 48h with dialysis membrane, obtains the molybdenum disulfide nano sheet aqueous solution；
B. it is in the preparation of the gold nanorods of positive potential
(4) take the chlorauric acid solution of 197 μ L0.05mol/L, be added to the cetyl trimethylammonium bromide of 0.1mol/L
(CTAB) stir under room temperature in the aqueous solution, add the silver nitrate solution of 30 μ L 4mmol/L, be stirring evenly and then adding into 70 μ
The ascorbic acid solution of L 111.7mmol/L, stops stirring after solution no color；
(5) it is rapidly added the sodium borohydride solution of 15 μ L 0.01mol/L in the solution of step (4), standing 3h is anti-for room temperature
Should；Take off layer after centrifugation 15min afterwards, 3 times repeatedly, lower sediment thing is disperseed in deionized water, to obtain gold nanorods water
Solution.
C. it is in electronegative molybdenum disulfide nano sheet and being combined in electropositive gold nanorods
(6) 10mg mercapto-polyglycol is added in the 10mL molybdenum bisuphide aqueous solution, under room temperature, reacts 24h；In two sulphur
Change and in molybdenum reaction solution, add the 10mL gold nanorods aqueous solution, mixing 24h obtains reactant liquor；Continuously add in reactant liquor afterwards
5mg mercapto-polyglycol (5000), reacts 24h；
(7) reaction finishes, and after centrifugation 10min, takes off a layer precipitate with deionized water dispersion, obtains molybdenum bisuphide/gold nano
Excellent nano composite material.
The second object of the present invention is to provide a kind of molybdenum disulfide nano/gold nanorods composite wood as described in one of purpose
Material, described composite has the photothermal conversion effect of near infrared region.
The third object of the present invention is to provide a kind of use of molybdenum bisuphide/gold nanorods composite as described in the two of purpose
On the way, described composite can be used for photo-thermal therapy.
The present invention has the advantages that：
(1) molybdenum bisuphide/gold nanorods composite that the present invention provides has preferable photothermal conversion performance；Further
Ground, after described molybdenum bisuphide/gold nanorods composite is modified by mercapto-polyglycol, its stability, dispersiveness and biofacies
Capacitive is also further enhanced；Advantage is had more in terms of the tumor thermal therapy of biomedical sector
(2) the preparation process process is simple of molybdenum bisuphide/gold nanorods composite that the application provides is easy to operate, equipment
Require low；The impurity content of the composite preparing is few, and yield is high, and in molybdenum bisuphide lamellar structure, gold nanorods
Combination density larger.
Brief description
The TEM figure of the molybdenum bisuphide that Fig. 1 prepares for embodiment 1/gold nanorods composite；
Fig. 2 is the electro kinetic potential analysis chart of molybdenum bisuphide, gold nanorods and molybdenum bisuphide/gold nanorods composite；
The x-ray diffraction pattern of the molybdenum bisuphide that Fig. 3 obtains for embodiment 1/gold nanorods composite；
The EDS energy spectrum diagram of the molybdenum bisuphide that Fig. 4 obtains for embodiment 1/gold nanorods composite；
The photothermal deformation test result of the molybdenum bisuphide that Fig. 5 obtains for embodiment 1/gold nanorods composite.
Specific embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that described enforcement
Example is only to aid in understanding the present invention, is not construed as the concrete restriction to the present invention.
Preparation example 1
A. it is in the preparation of the molybdenum disulfide nano sheet of negative potential
(1) weigh 500mg molybdenum disulfide powder (99%) to be placed in the round-bottomed flask that 10mL is dried, be passed through nitrogen, add
5mL 1.6mol/L dispersion n-BuLi in hexane, reacts 48h under room temperature；
(2), after reaction terminates, add hexane, diluting reaction solution, be centrifuged 10min；Disperse lower sediment with hexane, repeatedly
Centrifugation 2 times；
(3) take lower sediment disperse in aqueous, ultrasonic to bubble-free generation；Centrifugation 10min, removes lower floor, takes
Clear liquid, with the dialysis membrane dialysis 48h of 14kDa molecule interception, obtains the molybdenum disulfide nano sheet aqueous solution below 10 for the lamella.
Preparation example 2
A. it is in the preparation of the molybdenum disulfide nano sheet of negative potential
(1) weigh 500mg molybdenum disulfide powder (99%) to be placed in the round-bottomed flask that 10mL is dried, be passed through nitrogen, add
5mL 1.2mol/L is dispersed in the lithium chloride in hexamethylene, reacts 48h under room temperature；
(2), after reaction terminates, add hexamethylene, diluting reaction solution, be centrifuged 10min；Disperse lower sediment with hexamethylene,
It is centrifuged repeatedly 2 times；
(3) take lower sediment disperse in aqueous, ultrasonic to bubble-free generation；Centrifugation 10min, removes lower floor, takes
Clear liquid, with the dialysis membrane dialysis 48h of 14kDa molecule interception, obtains the molybdenum disulfide nano sheet aqueous solution below 10 for the lamella.
Preparation example 3
A. it is in the preparation of the molybdenum disulfide nano sheet of negative potential
(1) weigh 500mg molybdenum disulfide powder (99%) to be placed in the round-bottomed flask that 10mL is dried, be passed through nitrogen, add
5mL 4.8mol/L dispersion n-BuLi in hexane, reacts 48h under room temperature；
(2), after reaction terminates, add hexane, diluting reaction solution, be centrifuged 10min；Disperse lower sediment with hexane, repeatedly
Centrifugation 2 times；
(3) take lower sediment disperse in aqueous, ultrasonic to bubble-free generation；Centrifugation 10min, removes lower floor, takes
Clear liquid, with the dialysis membrane dialysis 48h of 14kDa molecule interception, obtains the molybdenum disulfide nano sheet aqueous solution below 10 for the lamella.
Preparation example 4
B. it is in the preparation of the gold nanorods of positive potential
(4) take the chlorauric acid solution of 197 μ L0.05mol/L, be added to the cetyl trimethylammonium bromide of 0.1mol/L
(CTAB) stir under room temperature in the aqueous solution, add the silver nitrate solution of 30 μ L 4mmol/L, be stirring evenly and then adding into 70 μ
The ascorbic acid solution of L 111.7mmol/L, stops stirring after solution no color；
(5) it is rapidly added the sodium borohydride solution of 15 μ L 0.01mol/L in the solution of step (4), standing 3h is anti-for room temperature
Should；Take off layer after centrifugation 15min afterwards, 3 times repeatedly, lower sediment thing is dispersed in water, obtains the gold nanorods aqueous solution.
Preparation example 5
B. it is in the preparation of the gold nanorods of positive potential
(4) take the chlorauric acid solution of 197 μ L 0.05mol/L, be added to the cetyl trimethylammonium bromide of 0.1mol/L
(CTAB) stir under room temperature in the aqueous solution, add the silver nitrate solution of 15 μ L 4mmol/L, be stirring evenly and then adding into 44 μ
The ascorbic acid solution of L 111.7mmol/L, stops stirring after solution no color；
(5) it is rapidly added the sodium borohydride solution of 10 μ L 0.01mol/L in the solution of step (4), standing 1h is anti-for room temperature
Should；Take off layer after centrifugation 15min afterwards, 3 times repeatedly, lower sediment thing is dispersed in water, obtains the gold nanorods aqueous solution.
Preparation example 6
B. it is in the preparation of the gold nanorods of positive potential
(4) take the chlorauric acid solution of 197 μ L0.05mol/L, be added to the cetyl trimethylammonium bromide of 0.1mol/L
(CTAB) stir under room temperature in the aqueous solution, add the silver nitrate solution of 45 μ L 4mmol/L, be stirring evenly and then adding into 264
The ascorbic acid solution of μ L 111.7mmol/L, stops stirring after solution no color；
(5) it is rapidly added the sodium borohydride solution of 25 μ L 0.01mol/L in the solution of step (4), room temperature stands 12h
Reaction；Take off layer after centrifugation 15min afterwards, 3 times repeatedly, lower sediment thing is dispersed in water, obtains the gold nanorods aqueous solution.
Embodiment 1
A kind of molybdenum dioxide/gold nanorods composite, with preparation example 1 obtain in electronegative molybdenum disulfide nano sheet
With preparation example 4 obtain in electropositive gold nanorods be raw material, be prepared via a method which：
(6) 10mg mercapto-polyglycol is added in the 10mL molybdenum bisuphide aqueous solution, under room temperature, reacts 24h；In two sulphur
Change and in molybdenum reaction solution, add the 10mL gold nanorods aqueous solution, mixing 24h obtains reactant liquor；Continuously add in reactant liquor afterwards
5mg mercapto-polyglycol (5000), reacts 24h；
(7) reaction finishes, and after centrifugation 10min, takes lower sediment water-dispersible, obtains molybdenum bisuphide/gold nanorods nanometer
Composite.
Structural characterization：
The molybdenum bisuphide that embodiment 1 is obtained/gold nanorods composite carries out transmission electron microscope (TEM) scanning, scanning knot
Fruit is as shown in Figure 1 (the TEM figure of the molybdenum bisuphide that Fig. 1 prepares for embodiment 1/gold nanorods composite)；Jenner in Fig. 1
The density ratio that rice rod is distributed on the lamella of molybdenum bisuphide is larger；Make the edge part of molybdenum bisuphide due to the absorption of gold nanorods
Position becomes more apparent upon, and the fold position of lamella equally makes gold nanorods more thickly be gathered in above because rejected region increases；Gold
The composite structure that nanometer rods are compounded in the formation of molybdenum bisuphide surface makes the contrast of molybdenum bisuphide become apparent from, and observes more square
Just；
The molybdenum bisuphide of embodiment 1, gold nanorods and molybdenum bisuphide/gold nanorods composite are carried out electro kinetic potential and divide
Analysis, (Fig. 2 is the electronic of molybdenum bisuphide, gold nanorods and molybdenum bisuphide/gold nanorods composite to analysis result as shown in Figure 2
Potentiometric analysis figure)；The potential of molybdenum bisuphide is -36.7mV as can be seen from Figure 2, and the potential of gold rod is+35.4mV,
Bi-material potential is completely contrary, and very different, and the potential of molybdenum bisuphide/gold nanorods composite be+
9.3mV, potential change and unicity reflect and are successfully prepared molybdenum bisuphide/gold nanorods composite；
The molybdenum bisuphide that embodiment 1 is obtained/gold nanorods composite carries out X-ray scanning, scanning result such as Fig. 3
(x-ray diffraction pattern of the molybdenum bisuphide that Fig. 3 obtains for embodiment 1/gold nanorods composite), from figure 3, it can be seen that system
The characteristic diffraction peak of the standby molybdenum bisuphide/gold nanorods composite obtaining includes molybdenum bisuphide (002) and gold nano simultaneously
Excellent (111), the characteristic diffraction peak of (200), and each diffraction peak intensity all has different degrees of reduction, shows to be successfully prepared two
Molybdenum sulfide/gold nanorods composite；
The molybdenum bisuphide that embodiment 1 is obtained/gold nanorods composite carries out EDS energy-spectrum scanning, scanning result such as Fig. 4
Shown (the EDS energy spectrum diagram of the molybdenum bisuphide that Fig. 4 obtains for embodiment 1/gold nanorods composite), from fig. 4, it can be seen that golden
(Au), molybdenum (Mo), the presence of sulphur (S) three kinds of elements, and signal strength signal intensity is very high, and molybdenum bisuphide/gold nanorods composite is described
In have the presence of three kinds of elements；Adopt copper mesh additionally, due to us as the substrate of material, so copper coin equally occurs in spectrogram
The signal of element.
Performance test：
The molybdenum bisuphide that embodiment 1 is obtained/gold nanorods composite carries out photothermal deformation test：
With equal volume, mutually synthermal water, as comparison, applies near infrared light to the molybdenum bisuphide aqueous solution, Jenner for experiment
The excellent aqueous solution of rice, molybdenum bisuphide/gold nanorods composite aqueous solution are irradiated respectively, and molten in different time node measurement
The trend of liquid temp change, test result such as Fig. 5 be (molybdenum bisuphide that Fig. 5 obtains for embodiment 1/gold nanorods composite
Photothermal deformation test result) shown in；From figure 5 it can be seen that increasing over time, the temperature of several components all has certain journey
The rising of degree；For water component, the temperature elevation amplitude of three kinds of materials is all higher, shows curing molybdenum sheet and Jin Bangdou
It is the very high material of photothermal conversion ability；In addition, compared with the material of two kinds of one-components, the answering of molybdenum bisuphide/gold nanorods
The temperature elevation amplitude of condensation material is bigger, reaches about 10 DEG C/10min near infrared light, shows that it has higher photo-thermal
Transfer capability.
Embodiment 2
A kind of molybdenum dioxide/gold nanorods composite, with preparation example 1 obtain in electronegative molybdenum disulfide nano sheet
With preparation example 4 obtain in electropositive gold nanorods be raw material, be prepared via a method which：
(6) 10mg sulfydryl ethylene glycol is added in the 10mL molybdenum bisuphide aqueous solution, under room temperature, reacts 24h；In curing
The 5mL gold nanorods aqueous solution is added, mixing 24h obtains reactant liquor in molybdenum reaction solution；5mg mercapto is continuously added afterwards in reactant liquor
Ethyl glycol (5000), reacts 24h；
(7) reaction finishes, and after centrifugation 10min, takes lower sediment water-dispersible, obtains molybdenum bisuphide/gold nanorods nanometer
Composite.
Embodiment 3
A kind of molybdenum dioxide/gold nanorods composite, with preparation example 1 obtain in electronegative molybdenum disulfide nano sheet
With preparation example 4 obtain in electropositive gold nanorods be raw material, be prepared via a method which：
(6) 10mg sulfydryl ethylene glycol is added in the 10mL molybdenum bisuphide aqueous solution, under room temperature, reacts 24h；In curing
The 40mL gold nanorods aqueous solution is added, mixing 24h obtains reactant liquor in molybdenum reaction solution；5mg is continuously added afterwards in reactant liquor
Sulfydryl ethylene glycol (5000), reacts 24h；
(7) reaction finishes, and after centrifugation 10min, takes lower sediment water-dispersible, obtains molybdenum bisuphide/gold nanorods nanometer
Composite.
Applicant states, the present invention illustrates detailed process equipment and the technological process of the present invention by above-described embodiment,
But the invention is not limited in above-mentioned detailed process equipment and technological process, that is, do not mean that the present invention has to rely on above-mentioned detailed
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
The interpolation of the equivalence replacement to each raw material of product of the present invention and auxiliary element, selection of concrete mode etc., all fall within the present invention's
Within the scope of protection domain and disclosure.
Claims (4)
1. a kind of preparation method of molybdenum bisuphide/gold nanorods composite is it is characterised in that methods described is：Will be in negative electricity
Property molybdenum disulfide nano sheet and be placed in the aqueous solution self assembly in electropositive gold nanorods and be combined, obtain molybdenum bisuphide/gold
Nanometer rod composite material, specifically includes following steps：
(1), under protective atmosphere, add in molybdenum disulfide powder and peel off agent dispersing liquid, carry out liquid phase stripping reaction；
(2) reaction finishes, and adds solvent to reactant liquor, and layering takes precipitation；
(3) precipitation of step (2) is dispersed in certain solvent, ultrasonic, centrifugation, takes supernatant to be dialysed, obtain curing
The molybdenum nanometer sheet aqueous solution；
(4) chlorauric acid solution is added in cetyl trimethylammonium bromide solution, stirs, add silver nitrate molten afterwards
Liquid, stirs, and adds ascorbic acid solution, continues stirring colourless to solution；
(5) add sodium borohydride solution, standing reaction, centrifugation layering in the solution of step (4), take lower sediment to be dispersed in water
In obtain the gold nanorods aqueous solution；
(6) the gold nanorods aqueous solution that step (5) obtains is added to mix in the molybdenum disulfide nano sheet aqueous solution obtaining to step (3)
Close, reacted afterwards；
(7) reaction finishes, centrifugation, takes lower sediment to be dispersed in water and obtains molybdenum bisuphide/gold nanorods composite；
Described remover is selected from n-BuLi and/or lithium chloride；
The mol ratio of described molybdenum bisuphide and remover is 1:(2～8)；
The described dispersion solvent peeling off agent dispersing liquid be selected from n-hexane, hexamethylene, any a kind in benzene saturated hydrocarbon solution or at least
2 kinds of combination；
The temperature of described liquid phase stripping reaction is 20～30 DEG C；Reaction time 5～144h；
The described solvent of step (2) peel off agent dispersing liquid described with step (1) dissolves each other.
2. the method for claim 1 is it is characterised in that the concentration of the described cetyl trimethylammonium bromide of step (4)
For 0.1mol/L；
The mol ratio of described gold chloride and silver nitrate is (164～54):1；
The mol ratio of described gold chloride and ascorbic acid is 1:(0.5～3)；
The mol ratio of described gold chloride and sodium borohydride is (98～39):1；
The time of described standing reaction is 1～12h.
3. the method for claim 1 is it is characterised in that the described molybdenum disulfide nano sheet of step (6) and gold nanorods
Mass ratio is 1:(1.25～10)；
The described reaction time is 3～48h.
4. the method for claim 1 is it is characterised in that the described mixed process of step (6) is added with mercapto-polyglycol；
In described mixed solution, the mass concentration of mercapto-polyglycol is 0.5～1mg/mL；
The molecular weight of described mercapto-polyglycol is 2000～10000.
Priority Applications (1)
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1978517A (en) * | 2005-11-30 | 2007-06-13 | 中国科学院兰州化学物理研究所 | Method for preparing metal silver molybdenum disulfide hybrid composite material |
| CN101979480A (en) * | 2010-10-27 | 2011-02-23 | 合肥学院 | Molybdenum disulfide nanosphere/titanium dioxide composite material and preparation method thereof |
| CN101623762B (en) * | 2008-07-09 | 2011-07-27 | 国家纳米科学中心 | Island-shaped porous tri-metal nano rod with gold core/silver-platinum alloy shell structure and method for preparing same |
| US8012278B2 (en) * | 2006-04-28 | 2011-09-06 | University of Pittsburgh—of the Commonwealth System of Higher Education | End-to-end joining of nanotubes |
| CN102825261A (en) * | 2012-09-29 | 2012-12-19 | 江南大学 | Binary plasma nanoparticle site specificity self-assembling method |
| CN102019179B (en) * | 2009-09-17 | 2012-12-26 | 国家纳米科学中心 | Gold-core/platinum-shell nano bar analogue enzyme solution and preparation method thereof |
| CN103440997A (en) * | 2013-08-26 | 2013-12-11 | 中国科学技术大学 | Metal double-hydroxide/molybdenum disulfide nano-composite material and preparation method and application thereof |
| CN104176781A (en) * | 2014-08-11 | 2014-12-03 | 华东师范大学 | Flaky nanometer molybdenum disulfide material, nanometer composite metal anticorrosive coating material and preparation method of flaky nanometer molybdenum disulfide material and nanometer composite metal anticorrosive coating material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008051302A2 (en) * | 2006-04-28 | 2008-05-02 | University Of Pittsburgh - Of The Commonwealth System Of Higher Education | End-to-end joining of nanotubes |
-
2014
- 2014-12-23 CN CN201410815045.4A patent/CN104525938B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1978517A (en) * | 2005-11-30 | 2007-06-13 | 中国科学院兰州化学物理研究所 | Method for preparing metal silver molybdenum disulfide hybrid composite material |
| US8012278B2 (en) * | 2006-04-28 | 2011-09-06 | University of Pittsburgh—of the Commonwealth System of Higher Education | End-to-end joining of nanotubes |
| CN101623762B (en) * | 2008-07-09 | 2011-07-27 | 国家纳米科学中心 | Island-shaped porous tri-metal nano rod with gold core/silver-platinum alloy shell structure and method for preparing same |
| CN102019179B (en) * | 2009-09-17 | 2012-12-26 | 国家纳米科学中心 | Gold-core/platinum-shell nano bar analogue enzyme solution and preparation method thereof |
| CN101979480A (en) * | 2010-10-27 | 2011-02-23 | 合肥学院 | Molybdenum disulfide nanosphere/titanium dioxide composite material and preparation method thereof |
| CN102825261A (en) * | 2012-09-29 | 2012-12-19 | 江南大学 | Binary plasma nanoparticle site specificity self-assembling method |
| CN103440997A (en) * | 2013-08-26 | 2013-12-11 | 中国科学技术大学 | Metal double-hydroxide/molybdenum disulfide nano-composite material and preparation method and application thereof |
| CN104176781A (en) * | 2014-08-11 | 2014-12-03 | 华东师范大学 | Flaky nanometer molybdenum disulfide material, nanometer composite metal anticorrosive coating material and preparation method of flaky nanometer molybdenum disulfide material and nanometer composite metal anticorrosive coating material |
Non-Patent Citations (1)
| Title |
|---|
| "Au的金属颗粒对二硫化钼发光增强";魏晓旭等;《物理学报》;20141130;第63卷(第21期);第217802-1～217802-5页 * |
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